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    • 专利摘要:
    A polymer electrolyte membrane comprising a microporouspolymer membrane having pores penetrating through the opposite sidesthereof. The microporous polymer membrane holds a mixture of apolymer and a molten salt at a weight ratio of 1/99 to 99/1 and/or a moltensalt. The polymer electrolyte membrane is inexpensive, durable, excellentin mechanical strength, excellent in structural retention in hightemperatures, and capable of stably holding a molten salt in its porouspolymer membrane structure, shows high heat resistance, and secures highionic conductivity in the absence of water or a solvent and is thereforeuseful in fuel cells, secondary batteries, electric double layer capacitors,electrolytic capacitors, and the like.
    公开号:EP1515346A1
    申请号:EP03760883
    申请日:2003-06-18
    公开日:2005-03-16
    发明作者:Masayuki c/o Ube Industries Ltd. KINOUCHI；Tetsuji C/O Ube Industries Ltd. Hirano；Nobuharu c/o Ube Industries Ltd. HISANO
    申请人:Ube Industries Ltd；
    IPC主号:C08J-5
    专利说明:
    [0001] The present invention relates to a polymer electrolyte membraneand, more particularly, a polymer electrolyte membrane useful in fuel cells,secondary batteries, electric double layer capacitors, electrolytic capacitors,etc. Background Art:
    [0002] Secondary batteries such as lithium ion batteries contain a porouspolymer membrane impregnated with an electrolytic solution as a separatorbetween a cathode and an anode. The electrolytic solution is volatile andflammable, which is problematical for safety when leakage occurs.
    [0003] It is known that ammonium salts of certain kinds, such asimidazolium salts and pyridinium salts, become liquid molten salts at100°C or lower, particularly around room temperature, and exhibit highionic conductivity at relatively low temperatures of 200°C or lower even inthe absence of water or an organic solvent. In view of the unique non-volatilityof these molten salts, application as an electrolyte of batteries,etc. has been studied. Being liquid, however, they are not easy to handle.In order to facilitate handling of the molten salts, several proposals havebeen made on a polymer electrolyte having a molten salt immobilized witha polymer.
    [0004] For example, JP-A-8-245828 discloses a composition comprisingan aliphatic quaternary ammonium salt of an organic carboxylic acid and apolymer, such as polyvinyl chloride, polyacrylonitrile or an aliphaticpolyether. JP-A-7-118480 discloses a combination of a room-temperaturemolten salt and a polymer of a vinyl monomer having an alkyl quaternaryammonium salt structure. JP-A-10-83821, JP-A-2000-3620, and JP-A-2000-11753propose an aliphatic molten salt type polymer synthesizedfrom an imidazolium compound and an acid or an acid monomer. A.Noda, et al., Electrochim Acta, vol. 45, 1265 (2000) and TP-A-11-86632 report a composition of a vinyl polymer and a molten salt. JP-A-10-265673discloses a polymer composite comprising a non-fluorine polymerand an ionic liquid. Because all these compositions use a polymer themain chain of which is composed mainly of an aliphatic hydrocarbongroup, they are inferior in durability characteristics including resistance tooxidation.
    [0005] JP-A-11-306858 discloses a composition of a vinylidene fluoridepolymer and an imidazolium salt, and J. Electrochem. Soc., vol. 147, 34(2000), Electrochimica Acta, vol. 46, 1703 (2001), and JP-A-11-86632teach compositions comprising an acid group-containing perfluoropolymerand a molten salt. A composition containing a fluoropolymer is expectedto have improved durability but is disadvantageous from the viewpoint ofcost and environmental burdens involved in the production offluoropolymers. It has therefore been demanded to develop aninexpensive and yet durable molten salt composition containing ahydrocarbon polymer.
    [0006] JP-A-11-86632 proposes a molten salt type polymer electrolytehaving a porous polymer solid or a polymer thin film made of a polyanionresin (having negative charges introduced) impregnated with animidazolium salt derivative. In the practice, however, the proposedtechnique involves such post-treatments as introduction of a carboxyl groupto a porous Teflon membrane using liquid ammonia and sodium orirradiation of a sodium polymethacrylate film with γ-rays to make the filmporous. Furthermore, a fluoropolymer has a lower glass transitiontemperature than room temperature and is therefore unreliable formechanical strength in high temperature, and an aliphatic polymer can havepoor durability against solvents or oxidation. The publication has nomention of the pore size of the porous polymer solid.
    [0007] JP-A-11-306858 proposes a solid polyelectrolyte composed of afluoropolymer matrix containing an imidazolium salt and a lithium salt. Itis virtually gel and liable to deformation under external pressure, which canpose a strength problem. A fluoropolymer has a lower glass transitiontemperature than room temperature and is therefore unreliable formechanical strength in high temperatures. Disclosure of the Invention:
    [0008] An object of the present invention is to provide an inexpensive anddurable polymer electrolyte membrane which has a clearly definedmicroporous structure stably holding a molten salt, exhibits excellentmechanical strength, maintains its structure even in high temperatures, andsecures high ion conductivity even in the absence of water or a solvent andprocesses of producing the polymer electrolyte membrane.
    [0009] The object is accomplished by the following polymer electrolytemembranes and processes of making the same.
    [0010] A polymer electrolyte membrane having a microporous polymermembrane having pores penetrating through the opposite sides thereof, themicroporous polymer membrane containing a mixture of a polymer and amolten salt at a weight ratio of 1/99 to 99/1 and/or a molten salt.
    [0011] A polymer electrolyte membrane having a microporous polymermembrane having pores penetrating through the opposite sides thereof, themicroporous polymer membrane containing a molten salt.
    [0012] A polymer electrolyte membrane comprising a microporouspolymer membrane having pores penetrating through the opposite sidesthereof and a mixture of a polymer and a molten salt at a weight ratio of1/99 to 99/1 held in the pores of the microporous polymer membrane.
    [0013] A polymer electrolyte membrane comprising a microporouspolymer membrane having pores penetrating through the opposite sidesthereof and a mixture of a polymer and a molten salt at a weight ratio of1/99 to 99/1 held in the pores and on both the opposite surfaces of themicroporous polymer membrane.
    [0014] A polymer electrolyte membrane comprising a microporouspolymer membrane having pores penetrating through the opposite sidesthereof, a molten salt held in the pores, and a layer comprising a mixture ofa polymer and a molten salt at a weight ratio of 1/99 to 99/1 provided onboth the opposite surfaces of the microporous polymer membrane.
    [0015] A process of producing a polymer electrolyte membrane containinga molten salt, comprising immersing a microporous polymer membranehaving pores penetrating through the opposite sides thereof in a molten saltto infiltrate the molten salt into the pores of the microporous polymermembrane.
    [0016] A process of producing a polymer electrolyte membrane containinga mixture of a polymer and a molten salt, comprising immersing amicroporous polymer membrane having pores penetrating through theopposite sides thereof in a solution of a mixture of a polymer and a moltensalt at a weight ratio of 1/99 to 99/1 in a solvent incapable of dissolving themicroporous polymer membrane to infiltrate the solution into themicroporous polymer membrane, and removing the solvent by drying tohave the mixture of the polymer and the molten salt held in themicroporous polymer membrane.
    [0017] A process of producing a polymer electrolyte membrane,comprising immersing a microporous polymer membrane having porespenetrating through the opposite sides thereof in a molten salt to infiltratethe molten salt into the pores of the microporous polymer membrane,applying a solution of a mixture of a polymer and a molten salt at a weightratio of 1/99 to 99/1 in a solvent incapable of dissolving the microporouspolymer membrane to both sides of the microporous polymer membrane,and removing the solvent by drying to form a layer of the mixture of thepolymer and the molten salt on both sides of the microporous polymermembrane. Brief Description of the Drawings:
    [0018] Fig. 1 is a graph showing temperature dependence of ionconductivity of the polymer electrolyte membranes prepared in Examples 1and 2.Fig. 2 is a graph showing temperature dependence of ionconductivity of the polymer electrolyte membrane prepared in Example 3.Fig. 3 is a graph showing temperature dependence of ionconductivity of the polymer electrolyte membrane prepared in Example 4.
    [0019] The microporous polymer membrane that can be used in the presentinvention is not particularly limited as long as it has open pores penetratingthrough both sides thereof. One which does not dissolve in the moltensalt to be held is preferred. When a solvent is used, a microporouspolymer membrane which does not dissolve in the solvent is preferred. The pores penetrating through the opposite sides may be either linear ornonlinear.
    [0020] Useful microporous polymer membranes include those of olefinpolymers such as polyethylene and polypropylene, and those of aromaticpolymers such as aromatic polyimide, aromatic polyether imide, aromaticpolysulfone, aromatic polyether sulfone, polyphenylene oxide,polyphenylene sulfide, aromatic polyether ketone, aromatic polyether etherketone, aromatic polyether ether ketone ketone, polybenzimidazole,polyquinoxaline, and polyphenylquinoxaline.
    [0021] Of the polymers making up the microporous polymer membranethose having a low glass transition temperature can have poor mechanicalstrength in high temperature applications even if they have a high meltingpoint. In order that the microporous structure should have heat resistanceand a small coefficient of linear expansion in high-temperature use so as toretain its porous structure, it is preferred to use a microporous polymermembrane made of a heat-resistant polymer that does not have a glasstransition temperature below 100°C, still preferably below 120°C,particularly preferably below 150°C.
    [0022] Microporous polymer membranes made of the above-recitedaromatic polymers can be mentioned as preferred examples of those madeof such heat-resistant polymers.
    [0023] Also useful are those made of aromatic heat-resistant polymers ofwhich the glass transition temperatures are so high that thermaldecomposition precedes glass transition, which makes glass transitiontemperature measurement difficult. Such aromatic heat-resistantpolymers include those described in Jyunji Furukawa, Sentan KobunshiZairyo Series 2 Koseino Hokozokukei Kobunshi Zairyo, Maruzen, Tokyo,52 (1990), such as poly(p-phenylene), polybenzothiazole, and poly(p-phenylenepyromellitic imide).
    [0024] The microporous polymer membrane which can be used in theinvention can be prepared by known techniques, such as solvent casting,extrusion, melting, and stretching. Commercially available microporouspolymer membranes may be utilized.
    [0025] For example, the microporous polyolefin membrane can beobtained by stretching a polyolefin film, such as a polyethylene film or a polypropylene film, to make the film porous. A commercially availableporous polyolefin film may be used as well.
    [0026] The microporous aromatic polymer membrane made of, forexample, an aromatic polyether sulfone can be prepared by a generalsolvent casting method. Specifically, an aromatic polyether sulfone isdissolved in a water-miscible solvent in a prescribed concentration, castingthe solution on a glass plate, immersing the coated glass plate in water toprecipitate the polymer, followed by drying to obtain a microporousaromatic polymer membrane. A commercially available one can be usedas well. The aromatic polyether sulfone may be synthesized in a knownmanner, or a commercially available product may be purchased.
    [0027] For use in the present invention, a microporous polymer membranemade of polyimide is particularly preferred in view of its heat resistance,dimensional stability especially in high temperature, solvent resistance, andthin film mechanical strength.
    [0028] Microporous polyimide membranes with pores penetrating throughboth sides thereof are disclosed, e.g., in JP-A-11-310658 and JP-A-2000-306568.They are prepared as follows. A solution is prepared from 0.3to 60% by weight of a polyimide precursor and 40 to 99.7% by weight of asolvent. The solution is cast in the form of film. In order to regulate therate of solvent exchange, a porous film of a polyolefin, etc. is superposedon the cast film. The resulting laminate is brought into contact with asolidifying solvent, thereby precipitating the polyimide precursor whileforming fine pores. The porous polyimide precursor membrane is thenconverted to the corresponding microporous polyimide membrane with finepenetrating pores by thermal or chemical imidization process.
    [0029] The polyimide precursor is a polyamic acid or a partially imidizedpolyamic acid obtained by polymerizing monomers as a tetracarboxylicacid component and a diamine component, preferably monomers belongingto aromatic compounds. The polyimide precursor cyclizes on heattreatment or chemical treatment to become a polyimide resin. The term"polyimide resin" as used herein means a heat-resistant polymer having adegree of imidization of about 50% or more.
    [0030] The solvent of the polyimide precursor solution includesp-chlorophenol, N-methyl-2-pyrrolidone (NMP), pyridine, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide,tetramethylurea, phenol, and cresol.
    [0031] The polyimide precursor is obtained by dissolving approximatelyequimolar amounts of a tetracarboxylic acid component and a diaminecomponent in the same organic solvent as used to dissolve the resultingpolyimide precursor and polymerizing them. The polyimide precursorpreferably has an inherent viscosity of 0.3 or greater, still preferably 0.5 to7 (at 30°C ;at a concentration of 0.5 g in 100 ml NMP). When thepolymerization is carried out at or above about 80°C, the polyimideprecursor imidized partially by cyclization is obtained.
    [0032] The diamine component includes p-phenylenediamine,m-phenylenediamine, 4,4'-diaminodiphenyl ether,3,3'-dimethyl-4,4'-diaminodiphenyl ether,3,3'-diethoxy-4,4'-diaminodiphenyl ether, and3,3'-dihydroxy-4,4'-diaminobiphenyl.Also included are diaminopyridine compounds, e.g., 2,6-diaminopyridine,3,6-diaminopyridine, 2,5-diaminopyridine, and 3,4-diaminopyridine.These diamine components can be used either individually or as a mixtureof two or more thereof. It is preferred that 3,3'-dihydroxy-4,4'-diaminobiphenylbe used in a proportion of at least 1 mol% based on thetotal diamine component. To use 1 mol% or more of3,3'-dihydroxy-4,4'-diaminobiphenyl is effective in producing amicroporous polymer membrane easy to impregnate with a polymer/moltensalt mixture.
    [0033] The tetracarboxylic acid component preferably includes3,3',4,4'-biphenyltetracarboxylic acid dianhydride and2,3,3',4'-biphenyltetracarboxylic acid dianhydride. Also useful are2,3,3',4'- or 3,3',4,4'-biphenyltetracarboxylic acid and a salt or esterderivative of 2,3,3',4'- or 3,3',4,4'-biphenyltetracarboxylic acid. Thesebiphenyltetracarboxylic acid compounds can be used as a mixture of two ormore thereof.
    [0034] The tetracarboxylic acid component may contain up to 10 mol%,preferably up to 5 mol%, based on the total tetracarboxylic acidcomponent, of other tetracarboxylic acid compounds than the above-describedbiphenyltetracarboxylic acid compounds, such as pyromellitic acid, 3,3',4,4'-benzophenonetetracarboxylic acid,2,2-bis(3,4-dicarboxyphenyl)propane,bis(3,4-dicarboxyphenyl) sulfone, bis(3,4-dicarboxyphenyl) ether,bis(3,4-dicarboxyphenyl) thioether, butanetetracarboxylic acid,and an anhydride, salt or ester derivative of these acids.
    [0035] The microporous polymer membrane that can be used in theinvention preferably has an average pore size of 0.01 to 50 µm, stillpreferably 0.05 to 10 µm. A membrane whose average pore size is toosmall is difficult to impregnate with a polymer/molten salt mixture or amolten salt. A membrane whose average pore size is too large is inferiorin mechanical strength and incapable of stably holding a polymer/moltensalt mixture or a molten salt.
    [0036] The microporous polymer membrane that can be used in theinvention preferably has a void of 10 to 90% by volume, still preferably 20to 80% by volume. With too small a void volume, the amount of apolymer/molten salt mixture or a molten salt that can be held is reduced,resulting in reduced ion conductivity. A membrane whose void is toolarge is inferior in mechanical strength and incapable of stably holding apolymer/molten salt mixture or a molten salt.
    [0037] The microporous polymer membrane that can be used in theinvention preferably has a linear expansion coefficient of 0.5 to 10 x 10-5/°C and an air resistance (Gurley) porosity of 10 to 1000 sec/100 cc. Themembrane thickness is selected according to the intended use. Forexample, the thickness is suitably 10 to 50 µm for lithium batteryapplication and 10 to 250 µm for fuel cell application.
    [0038] The polymer of the polymer/molten salt mixture that is held in themicroporous polymer membrane is not particularly limited as long as it canbe held together with a molten salt. Useful polymers include vinylpolymers, such as polymers having an aliphatic main chain, includingacrylic or methacrylic ester polymers, e.g., poly(methyl acrylate),poly(ethyl acrylate), poly(methyl methacrylate), andpoly(ethyl methacrylate); halogen-containing polymers, e.g., polyvinylchloride and polyvinylidene fluoride; styrene polymers, e.g., polystyreneand poly(α-methylstyrene); polyacrylonitrile; and polyvinyl acetate. Alsoincluded are aromatic polymers, such as aromatic polyether sulfone, aromatic polysulfone, aromatic polyether ketone, aromatic polyether etherketone, aromatic polyether ketone ketone, aromatic polyimide, andpolyphenylene oxide.
    [0039] The polymer preferably is cation exchange group-containg polymer.Preferred cation exchange groups include a sulfonic group, a carboxylgroup, and a phosphonic group.
    [0040] Such cation exchange group-containing polymers include cationexchange group-containing styrene polymers, such as poly(styrenesulfonicacid), poly(vinylbenzylsulfonic acid), a sulfo-containing styrene-(ethylene-butylene)-styrenetriblock copolymer and a sulfo-containing styrene-(ethylene-propylene)block copolymer that are described in JP-T-2002-509152and European Polymer Journal, vol. 36, 61 (2001), a carboxyl-containingstyrene-(ethylene-butylene)-styrene triblock copolymer anda carboxyl-containing styrene-(ethylene-propylene) block copolymer thatare described in Macromolecules, vol. 28, 8702 (1995) and EuropeanPolymer Journal, Vol. 36, 61 (2001), and phosphonic-containingpolystyrene described in JP-A-2000-11755; and cation exchange group-containingpolymers, such as polyacrylic acid, polymethacrylic acid, andpolyvinylsulfonic acid, and sulfo- or carboxyl-containingperfluoropolymers, such as Nafion®, Aciplex®, and Flemion®, have analiphatic main chain
    [0041] Also included are aromatic polymers, such as aromatic polyethersulfone, aromatic polysulfone, aromatic polyether ketone, aromaticpolyether ether ketone, aromatic polyether ketone ketone, aromaticpolyimide, and polyphenylene oxide, which contain cation exchangegroups. Examples are sulfo-containing aromatic polyether sulfonedescribed in JP-A-61-43630, J. Membr. Sci., vol. 83, 211 (1993), J. Polym.Sci., Part A, Polym. Chem., vol. 34, 2421 (1996), J. Polym. Sci., Part A,Polym. Chem., vol. 31, 853 (1993), and U.S. Patent Publication20010021764A1; carboxyl-containing aromatic polyether sulfone describedin Polymer, vol. 27, 1626 (1986), Polymer, vol. 42, 5973 (2001), andPolymer, vol. 34, 2836 (1993); sulfo-containing aromatic polyether ketonedescribed in JP-A-57-25328, JP-A-57-25328, JP-A-6-93114, J. Membr.Sci., vol. 199, 167 (2002), J. Membr. Sci., vol. 173, 17 (2000), Polymer,vol. 28, 1009 (1987), Solid State Ionics, vol. 106, 219 (1998), Br. Polym. J., vol. 17,4 (1985), and Polym. Int., vol. 50, 812 (2001); carboxyl-containingaromatic polyether ketone described in Macromolecules, vol.26, 5295 (1993); sulfo-containing polyimide described in Kobunshi GakkaiYokosyu (Polymer Preprints, Japan), vol. 51, 744-746 (2002); and sulfo-containingpolyphenylene oxide described in J. Appl. Polymer. Sci., vol.51, 1399 (1994), J. Appl. Polym. Sci., vol. 29, 4017 (1984), J. Appl.Polym. Sci., vol. 29, 4029 (1984), and J. Membr. Sci., vol. 146, 263 (1998).
    [0042] The polymer may be a copolymer, which may be a random, blockor graft copolymer.
    [0043] The cation exchange group-containing polymer preferably has anion exchange capacity of 0.3 to 7 meq/g, still preferably 0.5 to 7 meq/g.Where the ion exchange capacity is less than that lower limit, the polymertends to fail to retain a molten salt, allowing the molten salt to bleed out.
    [0044] The molten salt of the polymer/molten salt mixture that is held inthe microporous polymer membrane preferably has a melting point of100°C or lower, still preferably 80°C or lower, particularly preferably 60°Cor lower. Known molten salts can be used. The molten salt is composedof cation components and anion components. Preferred molten saltsinclude those that are liquid at room temperature, room-temperature moltensalts, and ionic liquids.
    [0045] The cation component composing the molten salt is preferably anammonium ion in view of molten salt's stability and the like. Cationshaving the following structures can be mentioned as examples.
    [0046] Cations having a cyclic structure preferably include those having animidazole ring, a triazole ring, a pyrrolidine ring, a pyridine ring, acyclohexane ring or a benzene ring. Each of these rings may besubstituted. Cations having a straight-chain or branched alkyl grouppreferably include those having an alkyl group containing 1 to 10 carbonatoms, e.g., methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl or hexyl. Preferred of the above cations are animidazolium cation, a triazolium cation,a tetraalkylammonium cation, a pyrrolidinium cation, and pyridiniumcation.
    [0047] The anion component composing the molten salt preferablyincludes sulfonic acid, a sulfonic acid compound, a carboxylic acid, and aninorganic acid. Specific examples are (CF3SO2)3C-, (CF3SO2)2N-, CF3SO3 -,C4F9SO3 -, CF3CO2 - , C3F7CO2 -, BF4 - ; PF6 - , ClO4 -, CH3SO3 -, CH3CO2 -, NO3 -,NO2 -, HSO3 -, and halide ions.
    [0048] Methods for synthesizing molten salts composed of the anion andcation components are known. For example, the molten salts aresynthesized by the methods described in Hiroyuki Ohno, LithiumNijidenchino Gijyutukakushinto Syoraitenbo, NTS Inc., Tokyo, p. 79(2001), R. Hagiwara et al., J. Fluorine Chem., vol. 105, 221 (2000), J. Sunet al., Electrochimica Acta., vol. 46, 1703 (2001), P. Bonhote et al., Inorg.Chem., vol. 35,1168 (1996), and D.R. McFarlane et al., Electrochim.Acta., vol. 45, 1271 (2000).
    [0049] More specifically, the molten salts are obtained by the reactionbetween a basic nitrogen-containing compound and/or a halogen saltthereof and an acid and/or a metal salt thereof.
    [0050] Examples of preferred molten salts are listed below.
    [0051] Trifluoromethanesulfonates, including1,3-dimethylimidazolium trifluoromethanesulfonate,1,3-diethylimidazolium trifluoromethanesulfonate,1,2-dimethylimidazolium trifluoromethanesulfonate,1,2-diethylimidazolium trifluoromethanesulfonate,1-ethyl-3-methylimidazolium trifluoromethanesulfonate,1-methyl-3-propylimidazolium trifluoromethanesulfonate,2-ethyl-1-methylimidazolium trifluoromethanesulfonate,1-ethyl-2-methylimidazolium trifluoromethanesulfonate,1,2,3-trimethylimidazolium trifluoromethanesulfonate,1,2-dimethyl-3-propylimidazolium trifluoromethanesulfonate,1-methylimidazolium trifluoromethanesulfonate,1-ethylimidazolium trifluoromethanesulfonate,1-vinylimidazolium trifluoromethanesulfonate, and2-methylimidazolium trifluoromethanesulfonate.
    [0052] Trifluoroacetates, such as 1,3-dimethylimidazolium trifluoroacetateand 1-ethyl-3-methylimidazolium trifluoroacetate.
    [0053] Tetrafluoroborates, such as 1,3-dimethylimidazolium tetrafluoroborate, 1,3-diethylimidazolium tetrafluoroborate,1,2-dimethylimidazolium tetrafluoroborate, 1,2-diethylimidazoliumtetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate,1-methyl-3-propylimidazolium tetrafluoroborate,2-ethyl-1-methylimidazolium tetrafluoroborate,1-ethyl-2-methylimidazolium tetrafluoroborate,1,2,3-trimethylimidazolium tetrafluoroborate,1,2-dimethyl-3-propylimidazolium tetrafluoroborate,1-methylimidazolium tetrafluoroborate,1-ethylimidazolium tetrafluoroborate,1-vinylimidazolium tetrafluoroborate,2-methylimidazolium tetrafluoroborate, and1-butylpyridinium tetrafluoroborate.
    [0054] Hexafluorophosphates, such as 1,3-dimethylimidazoliumhexafluorophosphate and 1-butyl-3-methylimidazoliumhexafluorophosphate.
    [0055] Tris(trifluoromethylsulfonyl)methides, such as1,3-dimethylimidazolium tris(trifluoromethylsulfonyl)methide,1,3-diethylimidazolium tris(trifluoromethylsulfonyl)methide,1,2-dimethylimidazolium tris(trifluoromethylsulfonyl)methide,1,2-diethylimidazolium tris(trifluoromethylsulfonyl)methide,1-ethyl-3-methylimidazolium tris(trifluoromethylsulfonyl)methide,1-methyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methide,2-ethyl-1-methylimidazolium tris(trifluoromethylsulfonyl)methide,1-ethyl-2-methylimidazolium tris(trifluoromethylsulfonyl)methide,1,2,3-trimethylimidazolium tris(trifluoromethylsulfonyl)methide,1,2-dimethyl-3-propylimidazolium tris(tripuoromethylsulfonyl)methide,1-methylimidazolium tris(trifluoromethylsulfonyl)methide, and2-methylimidazolium tris(trifluoromethylsulfonyl)methide.
    [0056] Methanesulfonates, such as 1,3-dimethylimidazoliummethanesulfonate, 1-methylimidazolium methanesulfonate,1-ethylimidazolium methanesulfonate, and 1-vinylimidazoliummethanesulfonate.
    [0057] Acetates, such as 1,3-dimethylimidazolium acetate,1-ethyl-3-methylimidazolium acetate, 1-methylimidazolium acetate, and 1-ethylimidazolium acetate.
    [0058] Nitrates, such as 1,3-dimethylimidazolium nitrate,1-ethyl-3-methylimidazolium nitrate, 1-methylimidazolium nitrate,1-ethylimidazolium nitrate, and 1-vinylimidazolium nitrate.
    [0059] Nitrites, such as 1,3-dimethylimidazolium nitrite and1-ethyl-3-methylimidazolium nitrite.
    [0060] Sulfites, such as 1,3-dimethylimidazolium sulfite,1-methylimidazolium sulfite, 1-ethylimidazolium sulfite, and1-vinylimidazolium sulfite.
    [0061] Chlorides, such as 1,3-dimethylimidazolium chloride,1-ethyl-3-methylimidazolium chloride, 1-methylimidazolium chloride,1-ethylimidazolium chloride, 1-vinylimidazolium chloride,1,2-dimethyl-1,2,4-triazolium chloride, and 1-butylpyridinium chloride.
    [0062] Bromides, such as 1,3-dimethylimidazolium bromide,1-ethyl-3-methylimidazolium bromide, 1-methylimidazolium bromide,1-ethylimidazolium bromide, 1-vinylimidazolium bromide, and1-butylpyridinium bromide.
    [0063] Bis(trifluoromethylsulfonyl)imides, such as1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide,1,3-diethylimidazolium bis(trifluoromethylsulfonyl)imide,1,2-dimethylimidazolium bis(trifluoromethylsulfonyl)imide,1,2-diethylimidazolium bis(trifluoromethylsulfonyl)imide,1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide,2-ethyl-1-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-ethyl-2-methylimidazolium bis(trifluoromethylsulfonyl)imide,1,2,3-trimethylimidazolium bis(trifluoromethylsulfonyl)imide,1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide,1-methylimidazolium bis(trifluoromcthylsulfonyl)imide,1-ethylimidazolium bis(trifluoromethylsulfonyl)imide,1-vinylimidazolium bis(trifluoromethylsulfonyl)imide, and2-methylimidazolium bis(trifluoromethylsulfonyl)imide.
    [0064] Of these molten salts, imidazolium salts are preferred for their lowviscosity at room temperature. Too viscous molten salts are difficult tohold in the microporous polymer membrane. Specifically, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate,1-ethyl-3-methylimidazolium tetrafluoroborate,1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-ethyl-3-methylimidazolium acetate,1-ethylimidazolium trifluoromethanesulfonate,1-ethylimidazolium tetrafluoroborate, 1-ethylimidazolium nitrate,1-ethylimidazolium bis(trifluoromethylsulfonyl)imide, and the like arepreferred.
    [0065] The polymer and molten salt mixture to be held in the microporouspolymer membrane has a polymer/molten salt weight ratio of 1/99 to 99/1,preferably 5/95 to 95/5. If the proportion of the molten salt is lower thanthat lower limit, the ion conductivity is unfavorably small. If it exceedsthe upper limit, the molten salt cannot be held stably.
    [0066] The content of the polymer/molten salt mixture is preferably 1 to99% by weight, still preferably 5 to 95% by weight. That content iscalculated using the following equation, in which W1 is the weight of amicroporous polymer membrane, and W2 is the weight of a polymerelectrolyte membrane, i.e., the weight of the microporous polymermembrane containing a polymer/molten salt mixture.The content of the mixture (wt%) = (W2-W1)/W2x100When the content of the mixture is smaller than that lower limit, the ionconductivity is reduced. When the content is larger than that upper limit,the effect of using a microporous polymer membrane on structure retentionis small.
    [0067] Where a molten salt alone is held in the microporous polymermembrane, the same molten salts as used in the polymer/molten saltmixture can be used.
    [0068] When only a molten salt is held in the porous polymer membrane,the molten salt content is preferably 1 to 90% by volume, still preferably 5to 90% by volume. The molten salt content can be calculated using thefollowing equation, where S and d mean the area and the thickness,respectively, of a microporous polymer membrane; and a and b representthe weight and the density, respectively, of an impregnating molten salt. Molten salt content (vol%) = a/(Sxdxb)x100When the molten salt content is smaller than that lower limit, the ionconductivity is small.
    [0069] The polymer electrolyte membrane according to the invention, inwhich the microporous polymer membrane with penetrating pores containsthe polymer/molten salt mixture and/or the molten salt, preferably includesthe following embodiments.
    [0070] A polymer electrolyte membrane having the molten salt held in thepores of the microporous polymer membrane.
    [0071] A polymer electrolyte membrane having the polymer/molten saltmixture held in the pores of the microporous polymer membrane.
    [0072] A polymer electrolyte membrane having the polymer/molten saltmixture held in the pores and on both surfaces of the microporous polymermembrane.
    [0073] A polymer electrolyte membrane having the molten salt held in thepores of the microporous polymer membrane and having a layercomprising the polymer/molten salt mixture formed on both surfaces of themicroporous polymer membrane.
    [0074] The polymer electrolyte membrane containing a molten salt can beproduced by immersing the microporous polymer membrane in a moltensalt. The molten salt is thus allowed to fill the pores of the microporouspolymer membrane and retained therein. If necessary, the molten salt isallowed to infiltrate under vacuum degassing and/or pressurizing toaccelerate displacement of gas in the pores of the microporous polymermembrane with the molten salt and filling the pores of the microporouspolymer membrane with the molten salt.
    [0075] If desired, the impregnating molten salt may be in the form of asolution in a solvent incapable of dissolving the microporous polymermembrane. In this case, the impregnated polymer membrane is dried byheating to remove the solvent.
    [0076] The solvent used to prepare the molten salt solution is notparticularly limited provided that the microporous polymer membrane doesnot substantially dissolve therein, including amides, sulfones, alcohols, ethers, and ketones. Examples of suitable solvents are water,N,N-dimethylformamide, N,N-dimethylacetamide,N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,dimethyl sulfoxide, sulfolane, diphenyl sulfone, tetrahydrofuran, methanol,ethanol, isopropyl alcohol, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, propylene glycol monomethyl ether,diethyl ether, and acetone.
    [0077] The temperature of the molten salt or the molten salt solution to beinfiltrated into the microporous polymer membrane is not particularlylimited as long as it is within a range of from the melting point of themolten salt and/or the melting point of the solvent to the boiling point ofthe solvent and also not higher than the melting or decompositiontemperature of the microporous polymer membrane and not higher than thedecomposition temperature of the molten salt. It is carried out at, forexample, a temperature of 0° to 300°C.
    [0078] The polymer electrolyte membrane containing a mixture of apolymer and a molten salt can be produced by immersing the microporouspolymer membrane in a solution of the polymer/molten salt mixture in asolvent incapable of dissolving the microporous polymer membrane toallow the solution to impregnate the microporous polymer membrane andremoving the solvent by drying. If necessary, the mixture solution isallowed to infiltrate with vacuum degassing and/or pressurizing toaccelerate displacement of gas in the pores of the microporous polymermembrane with the solution and filling the pores of the microporouspolymer membrane with the solution.
    [0079] The solvent for dissolving the polymer/molten salt mixture can bechosen with no limitation from among those useful in the preparation of themolten salt solution, provided that the microporous polymer membranedoes not substantially dissolve therein.
    [0080] The temperature of the polymer/molten salt solution to be infiltratedinto the microporous polymer membrane is not particularly limited as longas it is within a range of from the melting points of the molten salt and thesolvent to the boiling point of the solvent and also not higher than themelting or decomposition temperature of the microporous polymermembrane and not higher than the decomposition temperature of the molten salt. The impregnation is carried out at, for example, atemperature of 0° to 300°C.
    [0081] The polymer electrolyte membrane containing a molten salt in thepores of the microporous polymer membrane and having a layer of apolymer/molten salt mixture provided on both sides of the microporouspolymer membrane can be produced by immersing the microporouspolymer membrane in the molten salt to infiltrate the molten salt into thepores of the microporous polymer membrane, applying a solution of thepolymer/molten salt mixture in a solvent incapable of dissolving themicroporous polymer membrane to both sides of the microporous polymermembrane, and removing the solvent by drying to form a layer of thepolymer/molten salt mixture on both sides of the microporous polymermembrane. If desired, the molten salt is allowed to infiltrate with vacuumdegassing and/or pressurizing to accelerate displacement of gas in the poresof the microporous polymer membrane with the molten salt and filling thepores of the microporous polymer membrane with the molten salt.
    [0082] Furthermore, the impregnating molten salt may be in the form of asolution in a solvent incapable of dissolving the microporous polymermembrane. In this case, the impregnated polymer membrane is dried byheating to remove the solvent.
    [0083] The solvent used to prepare the molten salt solution and thepolymer/molten salt mixture solution can be chosen with no limitation fromamong those useful in the preparation of the molten salt solution used in theproduction of the polymer electrolyte membrane containing the molten salt,provided that the solvent does not substantially dissolve the microporouspolymer membrane.
    [0084] The temperature of impregnating the microporous polymermembrane with the molten salt and the temperature of applying thepolymer/molten salt mixture solution to the microporous polymermembrane are not particularly limited as long as they are within a range offrom the melting points of the molten salt and the solvent to the boilingpoint of the solvent and also not higher than the melting or decompositiontemperature of the microporous polymer membrane or not higher than thedecomposition temperature of the molten salt. The impregnation andapplication are carried out at, for example, a temperature of 0° to 300°C.
    [0085] In the production of the polymer electrolyte membrane of thepresent invention, a surface active agent can be used for the purpose offacilitating penetration of the molten salt and the polymer/molten saltmixture solution into the microporous polymer membrane. If desired, thepolymer electrolyte membrane can further contain an inorganic acid (e.g.,phosphoric acid, hypophosphorous acid or sulfuric acid) or a salt thereof, aperfluoroalkylsulfonic acid having 1 to 14 carbon atoms or a salt thereof, aperfluoroalkylcarboxylic acid having 1 to 14 carbon atoms or a salt thereof,a tertiary amine compound (e.g., imidazole, pyridine or an aliphatic tertiaryamine), or a salt of an alkali metal (e.g., lithium).
    [0086] According to the present invention, a polymer electrolytemembrane having an ion conductivity of, for example, 10-4 Scm-1 or higherat 100°C can appropriately be obtained.
    [0087] The effects of the present invention will be demonstrated by way ofExamples and Comparative Examples. In Examples and ComparativeExamples, measurements were made in accordance with the followingmethods. 1) Ion conductivityA membrane having been vacuum dried at 60°C for 16 hours wassandwiched between stainless steel plates having a radius of 0.65 cm andput into a closed container. The ionic conductivity was obtained bycomplex impedance measurement with FRD 1025 andPotentiostat/Galvanostat 283 supplied by Princeton Applied Research in athermostat set at a prescribed temperature. 2) Melting pointMeasured with DSC-7 supplied from Perkin-Elmer Inc. at a rate oftemperature rise of 10°/min in a helium stream. 3) ThicknessMeasured with a contact thickness gauge. 4) A percentage of voidA predetermined size of a piece was cut out of a microporouspolymer membrane, and the thickness and weight of the cut piece were measured. A percentage of void was obtained from the basis weightaccording to the following equation. In equation, S is the area of themicroporous polymer membrane; d is the membrane thickness; w is theweight measured; and D is the density of polyimide. The polyimide usedhad a density of 1.34.A percentage of void (%) = [1 - w/(S x d x D)] x 100 5) Average pore sizePore sizes within a range of 3.4 nm to 400 µm were measured bymercury intrusion porosimetry with Autoscan Prosimeter 60+500 fromYuasa Ionics Co., Ltd. An average of measured values in a range of3.4 nm to 1 µm was obtained. 6) Linear expansion coefficientMeasured with TMA-50 from Shimadzu Corp. during temperaturerise at a rate of 20°Cimin from 50° to 200°C in a nitrogen atmosphere. 7)TgCalculated from the temperature variance profile of dynamicviscoelasticity and loss tangent measured with RSA II supplied fromRheometric Scientific FE Ltd. while a sample was heated at a rate of3°C/min from -50° to 500°C in a tensile mode at a frequency of 5 Hz with a0.1 % strain. 8) ηsp/c (solution viscosity)Measurement was made on a 0.5 g/dl polymer solution in N-methyl-2-pyrrolidoneat 25°C with a Ubbellohde viscometer. Thesolution viscosity was calculated according to equation (1):(1) η sp/c = t s - t 0 t 0 ·1 c wherein ts is a solution flow time; t0 is a solvent flow time; and c is asolution concentration. 9) Ion exchange capacityA sample was stirred in a 0.01N sodium hydroxide aqueoussolution at room temperature for 16 hours, followed by filtration. Thefiltrate was titrated with a 0.01N hydrochloric acid aqueous solution to determine the amount of consumed sodium hydroxide, from which the ionexchange capacity was calculated. 10) Transmission electron microscopic observationA film was sliced in the thickness direction, and the slice wasobserved under JEM 200CX supplied from JEOL Ltd. at a magnification of90000 times.
    [0088] In a four-necked separable flask equipped with a stirrer, a nitrogeninlet tube, and a gas outlet tube were put N,N-dimethylacetamide as asolvent and 4,4'-diaminodiphenyl ether as a diamine component. Themixture was stirred at 40°C in a nitrogen atmosphere to make a solution.To the solution was added an equimolar amount, based on the diaminecomponent, of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride in severaldivided portions. The mixture was allowed to react at 40°C for about 12hours while stirring to obtain a viscous polyamic acid solution having asolid content of 9.1 wt%. The resulting solution was cast on a mirror-finishedSUS plate. A microporous polyolefin film (UP-3025, availablefrom Ube Industries, Ltd.) was superposed on the polyamic acid solutioncast film as a solvent exchange rate regulatory material. The laminatedfilm structure was immersed in methanol and then in water to obtain apolyamic acid microporous membrane. The membrane was fixed on a pintenter and heated in the atmosphere at 320°C to obtain microporouspolyimide membrane PI-1. The resulting membrane had the followingcharacteristics.Tg: 275°CAverage pore size: 0.18 µm.Void: 35%Air resistance (Gurley): 150 sec/100 ccThickness: 31 µmLinear expansion coefficient: 3.830 x 10-5/°C (SYNTHESIS EXAMPLE 2)
    [0089] In a four-necked separable flask equipped with a stirrer, a nitrogeninlet tube, and a gas outlet tube were put N,N-dimethylacetamide as asolvent and, as diamine components, 4,4'-diaminodiphenyl ether and 3,3'-dihydroxy-4,4'-diaminobiphenylat a molar ratio of 6/4. The mixture was stirred at 40°C in a nitrogen atmosphere to make a solution. To thesolution was added an equimolar amount, based on the total diaminecomponent, of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride in severaldivided portions. The mixture was allowed to react at 40°C for about 12hours while stirring to obtain a viscous polyamic acid solution having asolid content of 9.0 wt%. The resulting solution was cast on a mirror-finishedSUS plate. A microporous polyolefin film (UP-3025, availablefrom Ube Industries, Ltd.) was superposed on the polyamic acid solutioncast film as a solvent exchange rate regulatory material. The laminatedfilm structure was immersed in methanol and then in water to obtain amicroporous polyamic acid membrane. The membrane was fixed on a pintenter, and heated in the atmosphere at 320°C to obtain microporouspolyimide membrane PI-2 having the following characteristics.Tg: 290°CAverage pore size: 0.12 µm.Void: 68%Air resistance (Gurley): 66 sec/100 ccThickness: 76 µmLinear expansion coefficient: 4.634 x 10-5/°C (SYNTHESIS EXAMPLE 3)
    [0090] To a solution of 16 g of N-ethylimidazole in 20 ml of ethanol wasadded dropwise 25 g of trifluoromethanesulfonic acid at 0°C. Afterreturning to room temperature, the solution was stirred overnight and driedin vacuo at 60°C for 16 hours to give N-ethylimidazoliumtrifluoromethanesulfonate (hereinafter referred to as EtIm+TfS-) as acolorless transparent liquid. The melting point of the resulting salt(literature value: 7.8°C) was measured by DSC analysis. As a result,endothermic peaks were observed at 6.3°C and 21.0°C. (SYNTHESIS EXAMPLE 4)
    [0091] In a reactor were put 51.4 g of bis(4-fluorophenyl) sulfone, 25 g ofbis(4-hydroxyphenyl) sulfone, 18.9 g of 4,4'-biphenol, and 36 g ofpotassium carbonate. To the mixture were added 300 m of N,N-dimethylacetamideand 200 ml of toluene, followed by heating whilestirring in a nitrogen stream. The temperature was elevated up to 165°Cwhile removing produced water together with toluene. The stirring was continued for 3 hours at that temperature. The solution was poured into alarge quantity of water to precipitate a while solid, which was collected byfiltration, washed twice with hot water and once with methanol, and driedunder reduced pressure to obtain a copolymer. The solution viscosity ηsp/cof the resulting copolymer was 0.55.
    [0092] Ten grams of the resulting copolymer was dissolved in 100 ml of98% sulfuric acid, and the solution was stirred at room temperature for 24hours. The solution was poured into a large amount of water. Theprecipitated white solid was separated by filtration, washed twice with hotwater and once with methanol, and dried under reduced pressure to give asulfa-containing polyether sulfone. The resulting polymer had an ionexchange capacity of 1.73 mmol/g. A solution of the polymer in N,N-dimethylacetamidewas cast and dried to form a membrane. TEMobservation of the membrane revealed no phase separation structure,proving the polymer to be a random copolymer. (SYNTHESIS EXAMPLE 5)
    [0093] In 100 ml of 98% sulfuric acid was dissolved 10 g of acommercially available poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene)(weight average molecular weight: ca.20,800; number average molecular weight: 10,300; melting point: 322°C).The solution was stirred at room temperature for 45 hours and then pouredinto a large amount of water to precipitate a white solid. The solid wasseparated by filtration, washed with a large quantity of water until thewashing became neutral, and dried under reduced pressure to give a sulfo-containingpolyether ether ketone. The resulting polymer had an ionexchange capacity of 1.54 mmol/g. (SYNTHESIS EXAMPLE 6)
    [0094] In a four-necked flask equipped with a stirrer, a water contentmeter, a thermometer, and a nitrogen inlet tube were put 51.4 g of bis(4-fluorophenyl)sulfone, 50 g of bis(4-hydroxyphenyl) sulfone, and 36 g ofpotassium carbonate. Then, 300 ml of N,N-dimethylacetamide and200 ml of toluene were added thereto, followed by heating while stirring ina nitrogen stream. The temperature was elevated up to 165°C whileremoving produced water together with toluene. The stirring wascontinued for 3 hours at that temperature. The solution was poured into a large quantity of water to precipitate a white solid, which was collected byfiltration. The solid was washed twice with hot water and then once withmethanol and dried under reduced pressure to give hydrophobic segmentprepolymer (a). The resulting polymer (a) had a solution viscosity ηsp/c of0.42.
    [0095] To a mixture of 25.7 g of bis(4-fluorophenyl) sulfone, 18.9 g of4,4'-biphenol, and 18 g of potassium carbonate were added 150 ml of N,N-dimethylacetamideand 100 ml of toluene. The mixture was heated withstirring in a nitrogen stream up to 165°C while removing produced watertogether with toluene. The stirring was continued at that temperature for 3hours to prepare a polymer (b) solution. Separately, 42.6 g ofhydrophobic segment prepolymer (a) and 0.5 g of potassium carbonatewere added to a mixture of 150 ml of N,N-dimethylacetamide and 100 mlof toluene, and the mixture was heated in a nitrogen stream up to 165°Cwhile removing produced water together with toluene to prepare a solutionof a potassium salt of polymer (a). The resulting solution of thehydrophobic segment prepolymer (a) potassium salt was added to thepolymer (b) solution, and the mixture was stirred at 160°C for 1 hour.The mixed solution was poured into a large amount of water to precipitate awhite solid. The solid was collected by filtration, washed twice with hotwater and once with methanol, and dried in vacuo to obtain a copolymer.The resulting copolymer had a solution viscosity ηsp/c of 0.63.
    [0096] Ten grams of the resulting copolymer was dissolved in 100 ml of98% sulfuric acid. The solution was stirred at room temperature for 24hours, followed by pouring into a large quantity of water. The white solidthus precipitated was separated by filtration, washed twice with hot waterand once with methanol, and vacuum dried to yield sulfo-containingpolyether sulfone. The resulting polymer had a reduced viscosity of0.42 dl/g and an ion exchange capacity of 1.78 mmol/g. The hydrophilicsegment weight fraction was 0.49 as calculated by 1H-NMR analysis. Amembrane prepared by casting a solution of the sulfo-containing polyethersulfone in N,N-dimethylacetamide and drying revealed a phaseseparation structure under TEM observation, proving that the polymer to bea block copolymer. (EXAMPLE 1)
    [0097] A disk-shaped specimen having a diameter of 13 mm was cut out ofthe microporous polyimide membrane PI-1 prepared in Synthesis Example1. The specimen of the microporous polyimide membrane wasimpregnated with EtIm+TfS- obtained in Synthesis Example 3 by vacuumsuction. The vacuum suction was ended while both sides of the specimenwere wet. The excess EtIm+TfS- was wiped off both sides with waxedpaper. After the impregnation operation, the specimen became deeper inhue, indicating that EtIm+TfS- had been held in the fine pores. Thecontent of Etlm+TfS- was found to be 19 vol% as calculated from theweight gain of the specimen. The results of measurement of ionconductivity of the impregnated specimen are shown in Table 1 and Fig. 1.The ion conductivity at 150°C was as high as 2.5 x 10-4 Scm-1. Thespecimen after the ion conductivity measurement retained its original shapewith no changes in weight and thickness, proving stable in hightemperature. No liquid was found attached to the electrodes, showingsatisfactory capability of the membrane to hold EtIm+TfS-. (EXAMPLE 2)
    [0098] The same procedures as in Example 1 were followed, except forusing the microporous polyimide membrane PI-2 obtained in SynthesisExample 2. After impregnation with EtIm+TfS-, the specimen turneddeeper in hue, suggesting that Etlm+TfS- had been held in the fine pores.The EtIm+Tfs- content was found to be 66 vol% as calculated from theweight gain of the specimen. The results of measurement of ionconductivity of the impregnated specimen are shown in Table 1 and Fig. 1.The ion conductivity at 150°C was as high as 2.6 x 10-3 Scm-1. Thespecimen after the ion conductivity measurement retained its original shapewith no changes in weight and thickness, proving stable in hightemperature. No liquid was found attached to the electrodes, showingsatisfactory capability of the membrane to hold EtIm+TfS-. Temperature (°C) Ion Conductivity (Scm-1) Example 1 Example 2 50 5.1 x 10-5 4.7 x 10-480 1.1 x 10-4 7.1 x 10-4120 1.4 x 10-4 1.6 x 10-3150 2.5 x 10-4 2.6 x 10-3 (COMPARATIVE EXAMPLE 1)
    [0099] The microporous polyimide membrane PI-1 obtained in SynthesisExample 1 was used as such (without impregnation) as a specimen of ionconductivity measurement. No ion conductivity was exhibited. (COMPARATIVE EXAMPLE 2)
    [0100] The microporous polyimide membrane PI-2 obtained in SynthesisExample 2 was used as such (without impregnation) as a specimen of ionconductivity measurement. No ion conductivity was exhibited. (EXAMPLE 3)
    [0101] The sulfo-containing polyether sulfone obtained in SynthesisExample 4 and EtIm+TfS- obtained in Synthesis Example 3 were dissolvedin N,N-dimethylacetamide in concentrations of 6.72 wt% and 27.6 wt%,respectively (weight ratio: 20/80). A disk-shaped specimen having adiameter of 13 mm was cut out of the microporous polyimide membranePI-2 obtained in Synthesis Example 2. The specimen was impregnatedwith the resulting solution by vacuum suction. The vacuum suction wasended while both sides of the specimen were wet. After both sides of thespecimen were lightly wiped to remove the excess of the solution, it wasdried in vacuo at 60°C for 2 hours, at 120°C for 12 hours, and at 150°C for2 hours to remove the solvent. After the impregnation operation, thespecimen became deeper in hue and was tacky on both sides, indicatingthat the sulfo-containing polyether sulfone and EtIm+TfS- had been held inthe fine pores and on each side. The specimen's thickness increased from75 µm to 108 µm. The content of the sulfo-containing polyether sulfone and EtIm+TfS- was found to be 74 wt% as calculated from the weight gainof the specimen. The results of measurement of ion conductivity of theimpregnated specimen are shown in Table 2 and Fig. 2. The ionconductivity at 148°C was as high as 5.3 x 10-3 Scm-1. The specimen afterthe ion conductivity measurement retained its original shape with nochanges in weight and thickness, proving stable in high temperature. Noliquid was found attached to the electrodes, showing satisfactory capabilityof the membrane to hold the sulfo-containing polyether sulfone andEtIm+TfS-. Temperature (°C) Ion Conductivity (Scm-1) 50 1.2 x 10-380 2.5 x 10-3121 4.0 x 10-3148 5.3 x 10-3 (EXAMPLE 4)
    [0102] The sulfo-containing polyether sulfone obtained in SynthesisExample 6 and EtIm+TfS- obtained in Synthesis Example 3 were dissolvedin N,N-dimethylacetamide each in a concentration of 12 wt% (weight ratio:50/50).
    [0103] A disk-shaped specimen having a diameter of 13 mm was cut out ofthe microporous polyimide membrane PI-2 obtained in Synthesis Example2. The specimen was impregnated with EtIm+TfS- by vacuum suction.The vacuum suction was ended while both sides of the specimen were wet.The specimen became deeper in hue, which indicated that EtIm+TfS- hadbeen held therein. The above-prepared solution of the sulfo-containingpolyether sulfone and EtIm+TfS- was applied to both sides of theimpregnated specimen and dried in vacuo at 60°C for 2 hours, as 120°C for12 hours, and at 150°C for 2 hours to remove the solvent. A film of thesulfo-containing polyether sulfone and EtIm+TfS- was thus formed on eachside. The resulting specimen was tacky on both sides. The specimen'sthickness increased from 75 µm to 127 µm. The content of the sulfo-containingpolyether sulfone and EtIm+TfS- was found to be 79 wt% as calculated from the weight gain of the specimen. The results ofmeasurement of ion conductivity of the impregnated specimen are shownin Table 3 and Fig. 3. The ion conductivity at 150°C was as high as 2.3 x10-3 Scm-1. The specimen after the ion conductivity measurement retainedits original shape with no changes in weight and thickness, proving stablein high temperature. No liquid was found attached to the electrodes,showing satisfactory capability of the membrane to hold the sulfo-containingpolyether sulfone and EtIm+TfS-. Temperature (°C) Ion Conductivity (Scm-1) 49 1.1 x 10-479 3.6 x 10-4120 1.3 x 10-3150 2.3 × 10-3 Industrial Applicability:
    [0104] The present invention provides an inexpensive and yet durablepolymer electrolyte membrane which exhibits excellent mechanicalstrength, maintains its structure even in high temperatures, stably holds amolten salt in its porous polymer membrane structure, shows high heatresistance, and secures high ionic conductivity in the absence of water ora solvent and is therefore useful in fuel cells, secondary batteries, electricdouble layer capacitors, electrolytic capacitors, and the like and processesof producing the same.
    权利要求:
    Claims (22)
    [1] A polymer electrolyte membrane comprising a microporouspolymer membrane having pores penetrating through the opposite sidesthereof, the microporous polymer membrane containing a mixture of apolymer and a molten salt at a weight ratio of 1/99 to 99/1 and/or amolten salt.
    [2] The polymer electrolyte membrane according to claim 1, whereinthe microporous polymer membrane contains the molten salt.
    [3] The polymer electrolyte membrane according to claim 1, whereinthe microporous polymer membrane holds the mixture of the polymer andthe molten salt in the pores thereof.
    [4] The polymer electrolyte membrane according to claim 1, whereinthe microporous polymer membrane holds the mixture of the polymer andthe molten salt in the pores thereof and on both sides thereof.
    [5] The polymer electrolyte membrane according to claim 1, whereinthe microporous polymer membrane contains the molten salt in the poresthereof and has a layer comprising the mixture of the polymer and themolten salt provided on both sides thereof.
    [6] The polymer electrolyte membrane according to claim 1, wherein the microporous polymer membrane has an average pore size of 0.01 to50 µm.
    [7] The polymer electrolyte membrane according to claim 1, whereinthe microporous polymer membrane comprises a heat-resistant polymerhaving no glass transition temperature below 100°C.
    [8] The polymer electrolyte membrane according to claim 7, whereinthe heat-resistant polymer is a heat-resistant aromatic polymer.
    [9] The polymer electrolyte membrane according to claim 1, whereinthe microporous polymer membrane is a microporous polyimidemembrane.
    [10] The polymer electrolyte membrane according to claim 9, whereinthe polyimide constituting the microporous polyimide membranecomprises at least 1 mol% of 3,3'-dihydroxy-4,4'-diaminobiphenyl basedon the total diamine component.
    [11] The polymer electrolyte membrane according to claim 1, whereinthe microporous polymer membrane has a percentage of void of 10 to90% by volume.
    [12] The polymer electrolyte membrane according to claim 1, whereinthe polymer of the mixture is a cation exchange group-containing polymer.
    [13] The polymer electrolyte membrane according to claim 12,wherein the cation exchange group is a sulfonic group, a carboxyl groupor a phosphonic group, and the cation exchange group-containingpolymer has an ion exchange capacity of 0.3 to 7 meq/g.
    [14] The polymer electrolyte membrane according to claim 1, whereinthe molten salt has an ammonium ion as a cation component.
    [15] The polymer electrolyte membrane according to claim 1, whichhas a content of the mixture of the polymer and the molten salt of 1 to99% by weight.
    [16] The polymer electrolyte membrane according to claim 1, whichhas a content of the molten salt of 1 to 90% by volume.
    [17] A process of producing a polymer electrolyte membranecontaining a molten salt characterized by infiltrating the molten salt intopores of a microporous polymer membrane, comprising immersing themicroporous polymer membrane having pores penetrating through theopposite sides thereof in the molten salt.
    [18] The process of producing a polymer electrolyte membraneaccording to claim 17, wherein the molten salt is infiltrated into the pores of the microporous polymer membrane with vacuum degassing and/orpressurizing.
    [19] A process of producing a polymer electrolyte membranecontaining a mixture of a polymer and a molten salt characterized byhaving the mixture of a polymer and a molten salt held in a microporouspolymer membrane, comprising immersing the microporous polymermembrane having pores penetrating through the opposite sides thereof ina solution of the mixture of a polymer and a molten salt at a weight ratioof 1/99 to 99/1 in a solvent incapable of dissolving the microporouspolymer membrane and infiltrating the solution into the microporouspolymer membrane and removing the solvent by drying.
    [20] The process of producing a polymer electrolyte membraneaccording to claim 19, wherein the mixture is infiltrated into themicroporous polymer membrane with vacuum degassing and/orpressurizing.
    [21] A process of producing a polymer electrolyte membranecharacterized by forming a layer of the mixture of a polymer and a moltensalt on both sides of a microporous polymer membrane, comprisingimmersing the microporous polymer membrane having pores penetratingthrough the opposite sides thereof in a molten salt, infiltrating the moltensalt into the pores of the microporous polymer membrane, applying asolution of a mixture of a polymer and a molten salt at a weight ratio of 1/99 to 99/1 in a solvent incapable of dissolving the microporous polymermembrane to both sides of the microporous polymer membrane, andremoving the solvent by drying.
    [22] The process of producing a polymer electrolyte membraneaccording to claim 21, wherein the molten salt is infiltrated into the poresof the microporous polymer membrane, with vacuum degassing and/orpressurizing.
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    同族专利:
    公开号 | 公开日
    EP1515346B1|2008-09-03|
    AU2003244261A1|2004-01-06|
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    US7544445B2|2009-06-09|
    WO2004001771A1|2003-12-31|
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    JP2002207804||2002-07-17||
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    JP2002221156||2002-07-30||
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    PCT/JP2003/007740|WO2004001771A1|2002-06-19|2003-06-18|Polyelectrolyte membrane and production method therefor|
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